1842-38-2Relevant articles and documents
Tamagaki,Hatanaka
, p. 301 (1976)
Reaction of 1,3-bis(alkylseleno)allenes with diphenyl diazomethane
Shimizu,Miyasaka,Kamigata
, p. 7202 - 7204 (2001)
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Hydrolysis-Based Small-Molecule Hydrogen Selenide (H2Se) Donors for Intracellular H2Se Delivery
Bolton, Sarah G.,Chouinard, Julie E.,Garcia, Arman C.,Golledge, Stephen L.,Newton, Turner D.,Pluth, Michael D.,Zakharov, Lev N.
, p. 19542 - 19550 (2021/11/23)
Hydrogen selenide (H2Se) is a central metabolite in the biological processing of selenium for incorporation into selenoproteins, which play crucial antioxidant roles in biological systems. Despite being integral to proper physiological function, this reactive selenium species (RSeS) has received limited attention. We recently reported an early example of a H2Se donor (TDN1042) that exhibited slow, sustained release through hydrolysis. Here we expand that technology based on the P-Se motif to develop cyclic-PSe compounds with increased rates of hydrolysis and function through well-defined mechanisms as monitored by 31P and 77Se NMR spectroscopy. In addition, we report a colorimetric method based on the reaction of H2Se with NBD-Cl to generate NBD-SeH (λmax = 551 nm), which can be used to detect free H2Se. Furthermore, we use TOF-SIMS (time of flight secondary ion mass spectroscopy) to demonstrate that these H2Se donors are cell permeable and use this technique for spatial mapping of the intracellular Se content after H2Se delivery. Moreover, these H2Se donors reduce endogenous intracellular reactive oxygen species (ROS) levels. Taken together, this work expands the toolbox of H2Se donor technology and sets the stage for future work focused on the biological activity and beneficial applications of H2Se and related bioinorganic RSeS.
Bulky Selenium Ligand Stabilized Trans-Palladium Dichloride Complexes as Catalyst for Silver-Free Decarboxylative Coupling of Coumarin-3-Carboxylic Acids
Bhuvanesh, Nattamai,Himanshi,Joshi, Hemant,Kumar, Anil,Kumar, Sunil,Meena, Neha,Reddy, S. Rajagopala,Shinde, Vikki N.
, (2022/01/11)
This report describes the syntheses of three new trans-palladium dichloride complexes of bulky selenium ligands. These complexes possess a Cl?Pd?Cl rotor spoke attached to a Se?Pd?Se axle. The new ligands and palladium complexes (C1?C3) were characterized with the help of NMR, HRMS, UV-Vis., IR, and elemental analysis. The single-crystal structure of metal complex C2 confirmed a square planar geometry of complex with trans-orientation. The X-ray structure revealed intramolecular secondary interactions (SeCH—Cl) between chlorine of PdCl2 and CH2 proton of selenium ligand. Variable-temperature NMR data shows coalescence of diastereotopic protons, which indicates pyramidal inversion of selenium atom at elevated temperature. The relaxed potential energy scan of C2 suggests a rotational barrier of ～12.5 kcal/mol for rotation of chlorine atom through Cl?Pd?Cl rotor. The complex C3 possesses dual intramolecular secondary interactions (OCH2—Cl and SeCH2—Cl) with stator ligand. Molecular rotor C2 was found to be a most efficient catalyst for the decarboxylative Heck-coupling under mild reaction conditions. The protocol is applicable to a broad range of substrates with large functional group tolerance and low catalyst loading (2.5 mol %). The mechanism of decarboxylative Heck-coupling reaction was investigated through experimental and computational studies. Importantly the reaction works under silver-free conditions which reduces the cost of overall protocol. Further, the catalyst also worked for decarboxylative arylation and decarboxylative Suzuki-Miyaura coupling reactions with good yields of the coupled products.
Stereoselective Synthesis of Z-Vinyl Selenides Through the Reaction of Sodium Selenide with Organic Halides and Alkynes
Pistoia, Renan P.,Back, Davi F.,Zeni, Gilson
, p. 3794 - 3798 (2019/06/21)
A practical synthetic approach to the stereoselective synthesis of Z-vinyl selenides is described through the reaction of sodium selenide with organic halides, followed by the addition to alkynes. The reaction conditions were also successfully applied to
